Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/285—Nitrogen containing compounds
  • C08G18/286—Oximes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/285—Nitrogen containing compounds
  • C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4833—Polyethers containing oxyethylene units
  • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
  • C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/69—Polymers of conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides

Definitions

• the invention relates to the field of thermosetting epoxy resin compositions, in particular for bonding substrates with different thermal expansion coefficients, in particular in the shell of means of transport or white goods.
• thermosetting epoxy resin compositions have been known for a long time.
• An important field of application of thermosetting epoxy resin compositions is found in vehicle construction, in particular during bonding in the shell of means of transport or white goods. In both cases, after application of the epoxy resin composition, the bonded article is heated in an oven, whereby the thermosetting epoxy resin composition is cured.
• the curing step in the furnace at temperatures of 120-220 ° C. causes the two substrates to expand to different lengths.
• the bond reacts much more sensitive to static, dynamic and shock loads during life, which can lead to a weakening of the adhesive bond.
• thermosetting epoxy resin compositions for the structural bonding of substrates different coefficients of thermal expansion which on the one hand have sufficient mechanical properties for structural bonding and on the other hand to withstand the high stresses occurring during the thermosetting without failure of the structural connection.
• the present invention relates to the use of at least one toughener D for increasing the maximum elongation at elongation of a one-component thermosetting epoxy resin composition, the one-part thermosetting epoxy resin composition comprising:
• the weight ratio of the at least one epoxy resin A having an average of more than one epoxy group per molecule to the at least one toughener D is from 0.3 to 2.2, and wherein the toughener D is a terminally blocked polyurethane prepolymer of the formula (I);
• R 1 is a p-valent radical of an isocyanate-terminated linear or branched polyurethane prepolymer after removal of the terminal isocyanate groups
• p is a value from 2 to 8.
• R 2 is a blocking group which cleaves at a temperature above 100 ° C, where R 2 is not a substituent selected from the group consisting of
• R 12 is an alkylene group having 2 to 5 C atoms, which optionally has double bonds or is substituted, or for a phenylene group or for a hydrogenated phenylene group, in particular for e-caprolactam after removal of the NH proton.
• R 19 is bisphenols, after removal of a hydroxyl group, in particular bis-phenol-A, bis-phenol-F and 2,2'-diallyl-bisphenol-A.
• the maximum elongation Max. Strain is determined in a tensile shear test during cooling of a heated cured tensile shear sample.
• a “toughener” is understood in this document to be an addition to an epoxy resin matrix which, even at low additions of> 5% by weight, in particular> 10% by weight, based on the total weight of the epoxy resin compositions, causes a significant increase in the toughness and thus is able to absorb higher bending, tensile, impact or impact stress before the matrix enters or breaks.
• molecular weight is meant herein the molar mass (in grams per mole) of a molecule.
• average molecular weight denotes the number average molecular weight M n of an oligomeric or polymeric mixture of molecules, which is usually determined by GPC against polystyrene as standard.
• primary amino group in the present document denotes an NH 2 group which is bonded to an organic radical
• secondary amino group denotes an NH group, which is bonded to two organic radicals, which may also be part of a ring together. Accordingly, an amine having a primary amino group is referred to as a "primary amine", one having a secondary amino group is referred to as a “secondary amine” and one having a tertiary amino group as a “tertiary amine”.
• room temperature in this document refers to a temperature of 23 ° C.
• the "Da tension" was applied to a tensile shear test using a tensile tester in the laboratory method.
• the temperature profile in the convection oven was simulated by two thermocouples, which make it possible to measure the tensile shear stress in the area the adhesive surface with defined heating and cooling rates to temper. Since the cooling phase is the most critical, in this test, only during cooling a tension was applied over the tensile testing machine. Depending on the setting of the pulling speed on the tensile testing machine, it is possible to simulate variable stress cases that would occur with different substrate combinations.
• the temperature profile shown in FIG. 1 was defined for heating or cooling the samples. This results in start and end temperature and the temperature difference heating-up and
• Cooling rates have also been chosen at 40 ° C / min for the automotive industry.
• Equation 1 and 2 one obtains the thermal expansion for steel and aluminum according to Equation 4 and 5. This results during the heating phase a length expansion difference of 2.145mm, around which aluminum expands more than steel. Accordingly, the cured epoxy resin composition, which forms a cohesive connection, compensate for a shrinkage difference of 2.145mm during the cooling phase. Taking into account the cooling rate v A of 40 ° C
• the preparation sample is clamped in a tensile testing machine. For the time being, however, only the lower jaw is fixed.
• the clamping length is 100mm.
• thermocouples are pressed against the sample so that they are in contact with the adhesive surface.
• start and end temperature is set to 25 ° C and 190 ° C.
• heating and cooling rates 40 ° C / min is entered.
• the result of measurement is the force required to deform the tensile shear sample to break while cooling from 190 ° C to 25 ° C.
• a triple determination is carried out for each epoxy resin composition.
• the length expansion Max. Elongation is determined on the basis of the traversed path.
• the average values of the maximum length extension Max. Strain at maximum force are calculated from the measurement protocol
• Epoxy resin composition advantageous when a small maximum force must be applied.
• Particularly preferred such epoxy resin composition have a high maximum elongation Max. Strain and a small expended maximum force.
• Another interesting size is the force level at the end of the cooling phase, ie when reaching a length of 2.145mm. ever higher here is the force level, the more frozen tensions in the epoxy resin composition and irreversible deformations in the substrates are to be expected. Accordingly, the lowest possible level of force is an advantageous result here.
• the maximum elongation Max. Strain is determined in a tensile shear test during cooling of a heated cured tensile shear sample.
• the maximum longitudinal expansion Max. Elongation is measured in a tensile shear test at a tensile speed V tension of 0.52 mm / min.
• the maximum elongation Max. Elongation is determined as the elongation at the maximum force measured in the tensile shear test (maximum force).
• the maximum elongation Max. Strain in the tensile shear test is determined on the basis of the traversed traverse path.
• the temperature of the tensile shear test of the tensile shear test at the beginning of the measurement is 190 ° C and at the beginning of the measurement, the tensile shear sample is cooled at a cooling rate of 40 ° C / min to a temperature of 25 ° C and then left at that temperature.
• the tensile shear sample is heated to a temperature of 190 ° C at a heating rate of 40 ° C / min prior to commencement of the measurement.
• the tensile shear test is preferably a tensile shear test for determining the tensile shear strength according to DIN EN 1465.
• the tensile shear test is a tensile shear test with tensile shear specimens having the following characteristics:
• Adhesive surface of the cured one-component thermosetting epoxy resin composition with the masses 10mm x 25mm with a thickness of 1.5 mm, preferably 1.0mm.
• the steel sheets used are preferably made of hot-dip galvanized steel. Furthermore, these preferably have a yield strength of at least 420 MPa in order to minimize the influence of substrate deformation.
• the maximum length expansion Max. Elongation is preferably determined on the basis of the traversed path.
• the steel sheets are cleaned before applying the one-component thermosetting epoxy resin composition with heptane and then lubricated with 3g / m 2 with a thermoforming oil, in particular Anticorit PL3802-39S, oiled.
• a thermoforming oil in particular Anticorit PL3802-39S
• the one-part thermosetting epoxy resin composition is cured at 180 ° C for 35 minutes.
• the maximum elongation Max. Elongation > 2.145 mm, preferably> 2.2 mm, preferably> 2.5 mm, preferably> 2.8 mm, preferably> 3.0 mm, preferably> 3.5 mm, preferably> 4.0 mm.
• the measured maximum force is ⁇ 6000 N, preferably ⁇ 5000 N, preferably ⁇ 4500 N, preferably ⁇ 4000 N, preferably ⁇ 3500 N, preferably ⁇ 3000 N, preferably ⁇ 2500 N, preferably ⁇ 2000 N.
• the measured force when reaching the maximum longitudinal extent is Max. Elongation of 2,145 mm ⁇ 4,000 N, preferably ⁇ 3000 N, preferably ⁇ 2500 N, preferably ⁇ 2000 N, preferably ⁇ 1500 N, preferably ⁇ 1000 N, preferably ⁇ 800 N, preferably ⁇ 700 N.
• the epoxy resin A having on average more than one epoxide group per molecule is preferably an epoxide Liquid resin or a solid epoxy resin.
• the term "solid epoxy resin” is well known to the person skilled in the art and is used in contrast to "liquid epoxy resins". The glass transition temperature of solid resins is above room temperature, ie they can be comminuted at room temperature to form pourable powders.
• Preferred epoxy resins have the formula (II)
• substituents R 'and R "independently of one another are either Fl or CFb.
• the index s stands for a value of> 1.5, in particular from 2 to 12.
• Such solid epoxy resins are commercially available for example from Dow or Fluntsman or Flexion.
• the index s stands for a value of less than 1.
• s stands for a value of less than 0.2.
• Such epoxy resins are commercially available under the trade name EPN or ECN and Tactix® from Fluntsman or under the product series D.E.N. TM from Dow Chemical.
• the epoxy resin A is an epoxy liquid resin of the formula
• thermosetting epoxy resin composition contains both at least one epoxy liquid resin of the formula (II) with s ⁇ 1, in particular less than 0.2, and at least one solid epoxy resin of the formula (II) with s> 1.5, in particular of 2 until 12.
• the proportion of epoxy resin A is preferably 10 to 60 wt .-%, in particular 30 to 50 wt .-%, based on the total weight of the epoxy resin composition.
• the epoxy resin A is an aforementioned liquid epoxy resin.
• thermosetting epoxy resin composition contains at least one latent curing agent B for epoxy resins. This is activated by elevated temperature, preferably at temperatures of 70 ° C or more.
• the hardener B is particularly preferably dicyandiamide.
• the amount of latent curing agent B for epoxy resins is advantageously 0.1 to 30 wt .-%, in particular 0.2 to 10 wt .-%, preferably 1 to 10 wt .-%, particularly preferably 5 to 10 wt .-%, based on the Weight of the epoxy resin A.
• the thermosetting epoxy resin composition additionally contains at least one accelerator C for epoxy resins.
• accelerator C for epoxy resins are preferably substituted ureas, such as, for example, 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea (chlorotoluron) or phenyldimethylureas, in particular p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl-1, 1-dimethylurea (fenuron) or 3,4-dichlorophenyl-N, N-dimethylurea (diuron).
• 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea (chlorotoluron) or phenyldimethylureas in particular p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl-1, 1-dimethylurea (fenuron) or 3,4-dichloropheny
• imidazoles such as 2-isopropylimidazole or 2-hydroxy-N- (2- (2- (2-hydroxyphenyl) -4,5-dihydroimidazol-1-yl) ethyl) benzamide, imidazolines and amine complexes be used.
• the accelerator C for epoxy resins is selected from the list consisting of substituted ureas, imidazoles, imidazolines and amine complexes.
• the accelerator C for epoxy resins is particularly preferably selected from the list consisting of substituted ureas and amine complexes, in particular if the latent curing agent B is a guanidine, in particular dicyandiamide.
• the one-part thermosetting epoxy resin composition contains at least one toughener D.
• the tougheners D may be solid or liquid.
• the toughener D is a terminally blocked polyurethane polymer of the formula (I).
• R 1 is a p-valent radical of an isocyanate-terminated linear or branched polyurethane prepolymer after removal of the terminal isocyanate groups and p is from 2 to 8.
• R 2 is a blocking group which cleaves at a temperature above 100 ° C, where R 2 is not a substituent selected from the group consisting of
• R 12 is an alkylene group having 2 to 5 C atoms, which optionally has double bonds or is substituted, or represents a phenylene group or a hydrogenated phenylene group, in particular e-caprolactam after removal of the NH proton;
• R 19 for bisphenols after removal of a hydroxyl group, in particular bis-phenol-A, bis-phenol-F and 2,2'-diallyl-bisphenol-A, particularly preferably bis-phenol-A and bis-phenol-F, is.
• bisphenols is preferably understood to mean compounds which contain, as a common structural feature, two phenol rings linked via a carbon atom.
• R 2 independently represent a substituent selected from the group consisting of
• R 5 , R 6 , R 7 and R 8 each independently represent an alkyl or cycloalkyl or aralkyl or arylalkyl group
• R 9 , R 9 ' and R 10 each independently represent an alkyl or aralkyl or arylalkyl group or an alkyloxy or aryloxy or aralkyloxy group;
• R 11 is an alkyl group
• R 13 and R 14 each independently represent an alkylene group with 2 to
• R 15 , R 16 and R 17 each independently represent H or an alkyl group or an aryl group or an aralkyl group
• R 18 represents an aralkyl group having a substituted or unsubstituted aromatic group or a mononuclear substituted or unsubstituted aromatic group optionally having aromatic hydroxyl groups;
• R 4 is a radical of a primary or secondary hydroxyl group-containing aliphatic, cycloaliphatic, aromatic or araliphatic epoxide after removal of the hydroxy and epoxide groups;
• m is a value of 1, 2 or 3.
• R 2 independently of one another represent a substituent which is selected from the group consisting of
• R 18 are in particular phenols after removal of a
• phenols are in particular selected from the list consisting of phenol, cresol, 4-methoxyphenol (HQMME), resorcinol, pyrocatechol, cardanol (3-penta-decenylphenol (from cashew nut shell oil)) and nonylphenol.
• HQMME 4-methoxyphenol
• resorcinol resorcinol
• pyrocatechol cardanol (3-penta-decenylphenol (from cashew nut shell oil)) and nonylphenol.
• R 18 in particular, hydroxybenzyl alcohol and
• radicals R 2 are radicals which are selected from the group consisting of
• the radical Y in this case represents a saturated, aromatic or olefinically unsaturated hydrocarbon radical having 1 to 20 C atoms, in particular having 1 to 15 C atoms.
• Y in particular allyl, methyl, nonyl, dodecyl, phenyl, alkyl ethers, in particular methyl ethers, carboxylic acid esters or an unsaturated cis-alkyl radical having 1 to 3 double bonds are preferred.
• Y is selected from the group consisting of alkyl ethers, especially methyl ethers, and unsaturated cis-alkyl having 1 to 3 double bonds.
• an R 18 to phenols after removal of a flydroxyl group particularly preferred examples of such phenols are selected from the list consisting of 4-methoxyphenol (HQMME) and cardanol (3-pentadecenylphenol (from cashew nut shell oil)) ,
• R 5 , R 6 , R 7 , R 8 , R 9 , R 9 ' , R 10 , R 11 , R 15 , R 16 or R 17 is an alkyl group, this is in particular a linear or branched Ci-C2o Alkyl group.
• R 5, R 6, R 7, R 8, R 9, R 9 ', R 10, R 15, R 16 or R 17 is an aralkyl group, this group is in particular a group bonded through methylene aromatic group, especially a benzyl group ,
• R 5, R 6, R 7, R 8, R 9, R 9 'or R 10 is an alkylaryl group, this is particularly a group bonded through phenylene Ci to C2o alkyl group, such as tolyl or xylyl.
• the preparation of the terminally blocked polyurethane prepolymer of the formula (I) is carried out from the isocyanate-terminated linear or branched polyurethane prepolymer with one or more isocyanate-reactive compounds R 2 H. If several such isocyanate-reactive compounds are used, the reaction can be sequential or with a mixture these connections take place.
• the isocyanate-terminated polyurethane prepolymer on which R 1 is based can be prepared, in particular, from at least one diisocyanate or triisocyanate and from a polymer QPM with terminal amino, thiol or hydroxyl groups.
• Suitable diisocyanates are aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, in particular commercial products such as methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), tolidine diisocyanate (TODI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 2,5- or 2,6-bis (isocyanatomethyl) bicyclo [2.2.1] heptane, 1,5-naphthalene diisocyanate (NDI), dicyclohexylmethyl diisocyanate (H12MDI), p-phenylene diisocyanate (PPDI), m-tetramethylxylylene diisocyanate (TMXDI), etc. as well as their dimers.
• Preferred are HDI, IPDI, MDI or TD
• Suitable triisocyanates are trimers or biurets of aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, in particular the isocyanurates and biurets of the diisocyanates described in the preceding paragraph. Of course, suitable mixtures of di- or triisocyanates can be used.
• Suitable polymers QPM with terminal amino, thiol or hydroxyl groups are particularly suitable polymers QPM having two or three terminal amino, thiol or hydroxyl groups.
• the polymers QPM advantageously have an equivalent weight of 300-6000, in particular of 600-4000, preferably of 700-2200 g / equivalent of NCO-reactive groups.
• Preferred polymers QPM are polyols with average molecular weights between 600 and 6000 daltons selected from the group consisting of polyethylene glycols, polypropylene glycols, polyethylene glycol-polypropylene glycol block polymers, polybutylene glycols, polytetramethylene ether glycols, hydroxyl-terminated polybutadienes, hydroxyl-terminated butadiene-acrylonitrile copolymers and mixtures thereof, particularly preferred Polytetramethyleneetherglycole and hydroxyl-terminated polybutadiene.
• polytetramethylene ether glycols can be used.
• Polytetramethylene ether glycol is also referred to as polytetrahydrofuran or PTMEG.
• PTMEG may e.g. by polymerization of tetrahydrofuran, e.g. via acid catalysis.
• the polytetramethylene ether glycols are in particular diols.
• Polytetramethyleneether glycols are commercially available, e.g. As the PolyTHF ® - products from BASF as PolyTHF ® 2000, PolyTHF ® 2500 CO or CO PolyTHF ® 3000, the Terathane ® products from Invista BV or Polymeg® ® products from LyondellBasell.
• the OH functionality of the polytetramethylene ether glycol employed is preferably in the range of about 2, e.g. in the range of 1, 9 to 2,1. This is due to the cationic polymerization of the starting monomer tetrahydrofuran.
• Polytetramethylene ether glycols with OH numbers between 170 mg / KOH g to 35 mg KOH / g, preferably in the range from 100 mg KOH / g to 40 mg KOH / g, and very particularly preferably 70 to 50 mg KOH / g, are advantageous.
• the OH number determined by titrimetry according to DIN 53240.
• the hydroxyl number is determined by acetylation with acetic anhydride and subsequent titration of the excess acetic anhydride with alcoholic potassium hydroxide solution.
• the OH equivalent weights or the average molecular weight of the polytetramethylene ether glycol used can be determined from the hydroxyl numbers determined by titration.
• Polytetramethylene ether glycols advantageously used in the present invention preferably have an average molecular weight in the range from 600 to 5000 g / mol, more preferably 1000 to 3000 g / mol and particularly preferably in the range from 1500 to 2500 g / mol, in particular about 2000 g / mol , on.
• One or more hydroxy-terminated polybutadienes can be used. It is also possible to use mixtures of two or more hydroxy-terminated polybutadienes.
• Suitable hydroxy-terminated polybutadienes are, in particular, those which are prepared by free-radical polymerization of 1,3-butadiene, for example using an azonitrile or hydrogen peroxide as initiator. Hydroxy terminated polybutadienes are commercially available, such as the poly bd®- products from Cray Valley as poly bd® R45V, Polyvest ® HT Evonik and Hypro ® 2800X95HTB of Emerald Performance Materials LLC.
• the hydroxy-terminated polybutadiene preferably has an average molecular weight of less than 5,000, preferably in the range of 2,000 to 4,000 g / mol.
• the OH functionality of the hydroxy-terminated polybutadiene is preferably in the range from 1.7 to 2.8, preferably from 2.4 to 2.8.
• hydroxy-terminated polybutadienes having an acrylonitrile content of less than 15%, preferably less than 5% in particular preferably less than 1%, particularly preferably less than 0.1%. Most preferred are hydroxy-terminated polybutadienes free of acrylonitrile.
• the total content of polytetra methylene ether glycol and hydroxy-terminated polybutadiene is preferably at least 95% by weight and preferably at least 98% by weight.
• only polytetramethylene ether glycol and / or hydroxy-terminated polybutadiene are used as polyols.
• the weight ratio of polytetramethylene ether glycol to hydroxy-terminated polybutadiene is preferably in the range of 100/0 to 70/30, more preferably 100/0 to 60/40, more preferably 100/0 to 90/10, and most preferably 100/0.
• Winkelfellfestmaschine and the impact peel strength can be obtained. This can be seen for example in the comparison of Examples 2 and 3 in Table 3.
• the polyurethane prepolymer is prepared from at least one diisocyanate or triisocyanate and from a polymer QPM with terminal amino, thiol or hydroxyl groups.
• the preparation of the polyurethane prepolymer is carried out in a manner known to the person skilled in the polyurethane art, in particular by using the diisocyanate or triisocyanate in a stoichiometric excess with respect to the amino, thiol or hydroxyl groups of the polymer QPM.
• the polyurethane prepolymer having isocyanate end groups preferably has elastic character. It preferably exhibits a glass transition temperature Tg of less than 0 ° C.
• the weight ratio of the at least one epoxy resin A having on average more than one epoxide group per molecule to the at least one toughener D is from 0.3 to 2.2.
• a weight ratio of less than 0.3 is disadvantageous in that it causes the compositions to cure very slowly or not at all. Furthermore, in particular low values are obtained in modulus of elasticity, tensile strength and angular peel strength.
• a weight ratio of more than 2.2 is disadvantageous in that it gives the compositions having low impact peel strength and maximum elongation.
• the weight ratio of the at least one epoxy resin A having on average more than one epoxy group per molecule to the at least one toughener D is from 0.4 to 2.0, more preferably 0.5 to 1.8, most preferably 0.6 to 1.4. This is advantageous in that thereby the compositions have high values for peel peel strength and impact peel strength.
• the weight ratio of 0.3-2.2, in particular 0.4-2.2, 0.6-2.2, 1.0-2.2, 1.4-2.2, preferably 1.8-2.2 is advantageous in that thereby the compositions have high values for modulus of elasticity and tensile strength.
• the weight ratio of 0.4-2.0, in particular 0.4-1.8, preferably 0.4-1.4, particularly preferably 0.4-1.0 is advantageous in that the compositions have high values for the impact peel strength at -30 ° C., when R 2 is selected is made up of the group
• weight ratio of 0.3 to 2.0, in particular 0.3 to 1.8, 0.3 to 1.4, 0.3 to 1.0, 0.3 to 0.6, preferably 0.3 to 0.4, is.
• the composition additionally contains at least one filler F.
• This is preferably mica, talc, kaolin, wollastonite, feldspar, syenite, chlorite, bentonite, montmorillonite, calcium carbonate (precipitated or ground), dolomite, quartz, silicic acids (pyrogenic or precipitated), cristobalite, calcium oxide, aluminum hydroxide, magnesium oxide, ceramic hollow spheres, glass hollow spheres, organic hollow spheres, glass spheres, color pigments.
• the total proportion of the total filler F is 5-40% by weight, preferably 10-30% by weight, based on the total weight of the epoxy resin composition.
• the composition may contain a physical or chemical blowing agent such as that available under the tradenames Expancel TM from Akzo Nobel or Celogen TM from Chemtura or under the trade name Luvopor® from Lehmann & Voss.
• the proportion of blowing agent is typically 0.1 to 3 wt .-%, based on the total weight of the epoxy resin composition.
• the composition comprises less than 1 wt%, preferably less than 0.5 wt%, more preferably less than 0.3 wt%, most preferably less than 0.1 wt%, of physical or chemical blowing agent on the total weight of the epoxy resin composition.
• the composition additionally contains at least one epoxide group-carrying reactive diluent G.
• reactive diluents are known to the person skilled in the art.
• Preferred examples of epoxy group-bearing reactive diluents are:
• Glycidyl ethers of monofunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain CA-C30 alcohols e.g. Butanol glycidyl ether, hexanol glycidyl ether, 2-ethyl hexanol glycidyl ether, allyl glycidyl ether, tetrahydrofurfuryl and furfuryl glycidyl ether, trimethoxysilyl glycidyl ether, etc.
• Glycidyl ethers of difunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain C 2 -C 30 -alkanols for example ethylene glycol, butanediol, flexanediol, octanediolglycidyl ether, cyclohexanedimethanoldiglycidyl ether, neopentylglycol diglycidyl ether etc.
• Glycidyl ethers of trifunctional or polyfunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain alcohols such as epoxidized castor oil, epoxidized trimethylolpropane, epoxidized pentaerythrol or polyglycidyl ethers of aliphatic polyols, such as sorbitol, glycerol, trimethylolpropane, etc.
• - Glycidyl ethers of phenolic and aniline compounds such as phenylglycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, nonylphenol glycidyl ether, 3-n-pentadecenyl glycidyl ether (from cashew nut shell oil), N, N-diglycidylaniline etc.
• Epoxidized amines such as N, N-diglycidylcyclohexylamine etc.
• Epoxidized mono- or dicarboxylic acids such as neodecanoic acid glycidyl esters, glycidyl methacrylate, glycidyl benzoate, diglycidyl phthalate, tetra- and flexahydrophthalate, diglycidyl esters of dimeric fatty acids, etc.
• Epoxidized di- or trifunctional, low to high molecular weight polyether polyols such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc. Particularly preferred are hexanediol diglycidyl ethers, cresyl glycidyl ethers, p-tert-butylphenyl glycidyl ethers, polypropylene glycol diglycidyl ethers and polyethylene glycol diglycidyl ethers.
• the total proportion of epoxide group-carrying reactive diluent G is 0.1-15% by weight, preferably 0.1-5% by weight, more preferably 0.1-2% by weight, more preferably 0.2-1% by weight, based on the total weight of the epoxy resin composition.
• composition may comprise further constituents, in particular catalysts, stabilizers, in particular heat and / or light stabilizers, thixotropic agents, plasticizers, solvents, mineral or organic fillers, blowing agents, dyes and pigments, corrosion inhibitors, surfactants, defoamers and adhesion promoters.
• plasticizers are phenol alkyl sulfonic acid esters or benzenesulfonic acid N-butyl amide, such as are commercially available as Mesamoll® or Dellatol BBS from Bayer.
• Particularly suitable stabilizers are optionally substituted phenols, such as BHT or Wingstay® T (elixirs), sterically hindered amines or N-oxyl compounds, such as TEMPO (Evonik).
• Epoxy resin composition comprises:
• epoxy resin A having an average of more than one epoxide group per molecule; Preferably, it is 60-100 wt .-%, in particular 60-80 wt .-%, of the epoxy resin A is an epoxy liquid resin and at 0-40 wt .-%, in particular 20-40 wt .-%, of Epoxy A around an epoxy solid resin; at least one latent hardener for epoxy resins B, preferably selected from dicyandiamide, guanidines, anhydrides of polybasic carboxylic acids, dihydrazides, and aminoguanidines, and derivatives thereof, with dicyandiamide being preferred;
• At least one aforesaid toughener D at least one aforesaid toughener D, with preference being given to those which have been previously described as preferred tougheners D, the proportion of tougheners D being preferably 20-60% by weight, 25-55% by weight, 30-50% by weight. -%, particularly preferably 30-40 wt .-%, based on the total weight of the epoxy resin composition;
• a filler F selected preferably from the group consisting of wollastonite, calcium carbonate, calcium oxide, color pigments, in particular carbon black, and pyrogenic silicic acids, in particular calcium carbonate, calcium oxide and fumed silicas;
• 0.1 to 15% by weight preferably 0.1 to 5% by weight, particularly preferably 0.1 to 2% by weight, more preferably 0.2 to 1% by weight, based on the total weight of the
• Epoxy resin composition from an epoxy group-bearing reactive diluent G;
• the weight ratio of the at least one epoxy resin A having on average more than one epoxide group per molecule to the at least one toughener D is from 0.3 to 2.2, 0.4 to 2.0, particularly preferably 1.0 to 1.8. Further, it may be advantageous if the preferred one-part epoxy resin composition is greater than 80 weight percent, preferably greater than 90 weight percent, more preferably greater than 95 weight percent, more preferably greater than 98 weight percent, most preferably greater than 99 Weight%, based on the total weight of the epoxy resin composition, consists of the aforementioned constituents.
• An example of a particularly preferred composition is, for example, Example 13 in Table 5.
• the epoxy resin composition according to the invention has a viscosity at 25 ° C. of 100-10,000 Pa * s, in particular 500-5,000 Pa * s, preferably 1,000-3,000 Pa * s. This is advantageous in that this ensures good applicability.
• the viscosity is measured as described in the example section.
• Epoxy resin compositions which in the cured state:
• a tensile shear strength in particular measured according to DIN EN 1465, particularly preferably as described in the example part, of more than 10 MPa, more than 15 MPa, more than 20 MPa, and / or
• a tensile strength in particular measured according to DIN EN ISO 527, particularly preferably as described in the example section, of more than 10 MPa, more than 15 MPa, more than 20 MPa, and / or
• an elongation at break in particular measured according to DIN EN ISO 527, particularly preferably as described in the example section, of more than 10%, more than 20%, more than 30%, in particular 30-200%, particularly preferably 30-150% , and or
• -a impact peel strength in particular measured to ISO 11343, more preferably as described in the example section, of more than 30 N / mm, more than 40 N / mm, more than 60 N / mm at 23 ° C, and / or
• an angular peel strength in particular measured according to DIN 53281, particularly preferably as described in the example part, of more than 5 N / mm, more than 8 N / mm, more than 10 N / mm.
• the invention includes the use of at least one toughener D for increasing the maximum elongation at elongation of an aforementioned one-component thermosetting epoxy resin composition.
• the increase in the maximum elongation at elongation refers to the comparison with a one-component thermosetting epoxy resin composition, which in particular does not:
• the increase in the maximum longitudinal expansion is maximum elongation, compared to a one-component thermosetting epoxy resin composition, which does not in particular:
• thermosetting epoxy resin compositions are particularly suitable for use as one-component thermosetting adhesives, in particular as a thermosetting one-component adhesive in vehicle construction and sandwich panel construction.
• a one-component adhesive has a wide range of uses.
• this thermosetting one-component adhesives are feasible, which are characterized by a high impact strength, both at higher temperatures and at low temperatures.
• Such adhesives are needed for bonding heat stable materials.
• Heat-stable materials are materials which are dimensionally stable at a curing temperature of 100-220 ° C., preferably 120-200 ° C., at least during the curing time.
• metals and plastics such as ABS, polyamide, epoxy resin, polyester resin, polyphenylene ethers, fiber-reinforced plastics such as glass fiber and carbon fiber reinforced plastics.
• plastics are fiber-reinforced plastics.
• Preferred is the application in which at least one material is a metal.
• Particularly preferred use is the bonding of different metals, in particular metals with different thermal expansion coefficients (DO) and / or the bonding of metals with fiber-reinforced plastics, especially in the shell in the automotive industry.
• DO thermal expansion coefficients
• the preferred metals are, above all, steel, in particular electrolytically galvanized, hot-dip galvanized, oiled steel, Bonazink-coated steel, and subsequently phosphated steel, and aluminum, in particular in the variants typically occurring in the automobile industry.
• Such an adhesive is in particular first contacted with the materials to be bonded at a temperature of between 10 ° C. and 80 ° C., in particular between 10 ° C. and 60 ° C., and later cured at a temperature of typically 130-220 ° C, preferably 140-200 ° C, more preferably 150-190 ° C. From such a previously mentioned use results in a glued article.
• Such an article is preferably a vehicle or a part of a vehicle.
• a further aspect of the present invention therefore relates to a bonded article obtained from the aforementioned use.
• sealing compositions can also be realized with a composition according to the invention.
• the novel compositions are not only suitable for the automotive industry but also for other applications. Particularly noteworthy are related applications in transport engineering such as ships, trucks, buses or rail vehicles or in the construction of consumer goods such as washing machines.
• composition materials are used at temperatures between typically 120 ° C and -40 ° C, preferably between 100 ° C and -40 ° C, in particular between 80 ° C and -40 ° C used.
• the isocyanate content was determined in wt .-% by means of a back titration with excess di-n-butylamine and 0.1 M hydrochloric acid. All determinations were performed semi-manually on a Mettler-Toledo DL50 Graphix titrator with automatic potentiometric end point determination. For this purpose, in each case 600-800 mg of the sample to be determined were dissolved with heating in a mixture of 10 ml of isopropanol and 40 ml of xylene and then reacted with a solution of dibutylamine in xylene. Excess di-n-butylamine was titrated with 0.1 M hydrochloric acid and the isocyanate content was calculated therefrom.
• the maximum elongation (Max. Elongation) and the Maximum Force (Max. Force) were determined as described above under "Description Measurement Method for Maximum Elongation (Maximum Elongation) and Maximum Force". For each epoxy resin composition, a triple determination was made. The maximum length expansion Max. Elongation was determined on the basis of the traversed path. For the evaluation of the measurement, the average values of the maximum length extension Max. Strain at maximum force were determined from the measurement protocol
• Curing conditions a) 35 minutes at 175 ° C oven temperature.
• the tensile shear strength was determined on a tractor at a tensile speed of 10 mm / min in a 3-fold determination according to DIN EN 1465.
• Test panels a 130 x 25 mm were prepared from steel DC-04 + ZE (thickness 0.8 mm). Test panels were unwound at a height of 30 mm with a suitable punching machine (90 °). The cleaned surfaces of 100 ⁇ 25 mm back-lubricated with Anticorit PL 3802-39S were bonded to the adhesive with glass beads as spacers in a layer thickness of 0.3 mm and cured for a residence time of 35 minutes after reaching a furnace temperature of 175 ° C. The peel strength was determined on a tractor with a pulling speed of 100 mm / min in a 2-fold determination as a peel force in N / mm in the range of the traverse path of 1/6 to 5/6 path length.
• the specimens were produced with the adhesive and steel DC04 + ZE with the dimensions 90 x 20 x 0.8 mm.
• the adhesive surface was 20 ⁇ 30 mm with a layer thickness of 0.3 mm and glass beads as spacers.
• RT 23 ° C., -30 ° C.
• As impact peel strength the average force in N / mm under the measurement curve from 25% to 90% according to IS011343.
• Viscosity measurements on the adhesives were made 1d after preparation on a rheometer type MCR 101 manufacturer Anton Paar oscillatory using a plate-plate geometry at a temperature of 25 ° C and 50 ° C with the following parameters: 5 Hz, 1 mm gap, Plate-to-plate distance 25 mm, 1% deformation.
• Example 1 Impact modifier SM1 (phenol [1.2 eq.] As
• 225 g of PolyTHF 2000, 225 g of poly bd R45V and 2.25 g of BHT as stabilizer were dewatered under reduced pressure at 90 ° C. for 1 h with minimal stirring. Subsequently, 90.83 g of isophorone diisocyanate (IPDI) and 0.059 g of dibutyltin dilaurate (DBTDL) were added. The reaction was carried out under vacuum at 90 ° C for 2 hours with moderate agitation to obtain an isocyanate-terminated polymer: Measured free NCO content: 3.05%.
• IPDI isophorone diisocyanate
• DBTDL dibutyltin dilaurate
• Example 2 impact modifier SM2 (4-methoxyphenol [1.2 eq.] As blocking agent, PolyTHF2000 / PolyBD R45V as backbone)
• DBTDL dibutyltin dilaurate
• HQMME 4-methoxyphenol
• Example 3 impact modifier SM3 (4-methoxyphenol [1,2eq.] As blocking agent, PolyTHF 2000 as backbone)
• DBTDL dibutyltin dilaurate
• HQMME 4-methoxyphenol
• Example 5 impact modifier SM5 (3,5-dimethylpyrazole [1,2eq.] As blocking agent, PolyTHF 2000, poly bd R45V as backbone)
• 225 g of PolyTHF 2000, 225 g of poly bd R45V and 2.25 g of BHT as stabilizer were dewatered under reduced pressure at 90 ° C. for 1 h with minimal stirring. Subsequently, 77.82 g of isophorone diisocyanate (IPDI) and 0.058 g of dibutyltin dilaurate (DBTDL) were added. The reaction was carried out under vacuum at 90 ° C for 2 hours with moderate agitation to obtain an isocyanate-terminated polymer: Measured free NCO content: 3.08%.
• IPDI isophorone diisocyanate
• DBTDL dibutyltin dilaurate
• Example 6 Impact modifier SM6 (dibutylamine [1.0eq.] As blocking agent, PolyTHF 2000, poly bd R45V as backbone)
• DBTDL dibutyltin dilaurate
• 37.52 g of dibutylamine were added to the NCO-terminated polymer obtained, and the isocyanate groups were reacted for 3 hours under reduced pressure at 70.degree. Measured free NCO content: 0.0%
• Example 7 Impact modifier SM7 (MEKO [1.2 eq.] As
• DBTDL dibutyltin dilaurate
• MEKO 2-butanoxime
• Example 8 Impact modifier SM8 (2,2-diallylbisphenol A [1,2 eq.] As blocking agent)
• Free NCO content measured next day at RT 0.36%.
• Example 9 Impact modifier SM9 (caprolactam [1.2 eq.] As blocking agent)
• DBTDL dibutyltin dilaurate
• caprolactam 47.01 g
• the impact modifiers SM1 to SM9 prepared in Examples 1 to 9 were each used to prepare epoxy resin compositions shown in Table 2.
• SM-X refers to the above-prepared impact modifiers SM1, SM2, etc. Table 2
• the respective epoxy resin compositions were mixed in a batch size of 350 g in a planetary mixer.
• the mixing box was filled with the liquid components followed by the solid components and mixed at 70 ° C under vacuum. During the mixing process (about 45 minutes) the vacuum was broken several times and the mixing tool was stripped off. After obtaining a homogeneous mixture, the epoxy resin composition was filled into cartridges and at
• Tables 3 and 4 show the results of the evaluation of the obtained epoxy resin compositions with the impact modifiers SM1-9.
• compositions 10-24 Compositions 10-24
• the impact modifiers SM2, SM3 and SM4 were in
• bisphenol A epoxy resin is a mixture of 2 parts of liquid epoxy resin based on bisphenol A and one part of solid epoxy resin based on bisphenol A.
• Tables 6-8 show the results of the evaluation of the obtained adhesives 10-25 with the impact modifiers SM2, SM3 and SM4.

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